Ammonia → HCID 13409302, compound

HRID 536660Notes

Reaction equation

HRID 536660 reaction equation
[CH2:1]([CH:8]1[N:13]([CH3:14])[CH:12]([CH3:15])[CH2:11][C:10]([CH3:16])=[CH:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(C1CC(C)=CC(C)N1C)C1C=CC=CC=1.N>O.Br.C(O)(=O)C>[CH3:14][N:13]1[CH:12]([CH3:15])[CH2:11][C:10]2([CH3:16])[CH2:9][CH:8]1[CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=12

Participants

7

Reactant 3

HCID 222AmmoniaHCID 58123857HCID 58123857, compoundHCID 58123921HCID 58123921, compound

Product 1

HCID 13409302HCID 13409302, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 260Hydrogen BromideSolvent2×HCID 962WaterSolvent

Procedure

A mixture of 6-benzyl-1,2,4-trimethyl-1,2,3,6-tetrahydro-pyridine and 2-benzyl-1,4,6-trimethyl-1,2,3,6-tetrahydropyridine (from Example LV, 11.7 g) is combined with 48% HBr in water (30 mL) and 33% HBr in acetic acid (20 mL). The mixture is heated to reflux temperature and stirred at this temperature for 4 d. After cooling to ambient temperature, aqueous ammonia (32%, 45 mL) is carefully added and the resulting mixture is extracted with Et2O (3×50 mL). The combined organic extracts are extracted with 2 M hydrochloric acid (3×50 mL), the combined aqueous extracts are basified using 32% aqueous ammonia (20 mL), and the basic aqueous phase is extracted with Et2O (3×50 mL). The combined organic extracts are dried (MgSO4), the solvent is removed, and the residue is purified by chromatography on silica gel (EtOAc/MeOH/NH395:5.0.5->75:25:2.5). The title compound obtained thereafter is dissolved in iPrOH and treated with HCl in iPrOH to precipitate the HCl salt of the title compound from the iPrOH solution.

Workup

  1. temperatureThe mixture is heated
  2. temperatureto reflux temperature
  3. extractionthe resulting mixture is extracted with Et2O (3×50 mL)
  4. extractionThe combined organic extracts are extracted with 2 M hydrochloric acid (3×50 mL)
  5. extractionthe basic aqueous phase is extracted with Et2O (3×50 mL)
  6. dry with materialThe combined organic extracts are dried (MgSO4)
  7. customthe solvent is removed
  8. customthe residue is purified by chromatography on silica gel (EtOAc/MeOH/NH395:5.0.5->75:25:2.5)

Sources & evidence

ORD record
ord-80aa73c8c4574b4caa05ddd524caf759
Source dataset
uspto-grants-2014_10
Patent number
US08859580B2

Reaction notes

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